Acrylate and methacrylate monoesters of pentaerythritol and pentaerythritol orthoesters and polymers and copolymers derived therefrom

ABSTRACT

Acrylate and methacrylate monoesters of pentaerythritol and pentaerythritol orthoesters are provided. These orthoesters are especially useful as monomers for the preparation of polymers and copolymers having a variety of industrial applications.

This is a division of application Ser. No. 248,183 filed Mar 30, 1981now U.S. Pat. No. 4,405,798.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to monoesters derived from ethylenicallyunsaturated carboxylic acids and polyhydroxy alcohols and to polymersand copolymers prepared from such monoesters.

2. Description of the Prior Art

Multifunctional polyol derivatives of acrylic or methacrylic acid estersof polyols in which at least two hydroxyl groups are esterified andsynthetic resins prepared from such derivatives are known. U.S. Pat. No.3,943,103 describes a polyfunctional reactive solvent which conferscrosslink density to a radiation curable resin composition containing alow molecular weight vinyl acetate polymer and a monofunctional acrylateester. The polyfunctional reactive solvent is polyacrylate ester havingfrom 2 to 6 acrylyl groups such as pentaerythritol di-, tri-, ortetra-acrylate. The monofunctional ester is derived from acrylic ormethacrylic acid and a monohydroxyl compound, e.g., methyl methacrylate,butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethylacrylate, dicyclopentenyl acrylate, (methylcarbamyl)ethyl acrylate,2-phenoxyethyl acrylate, 2-methoxyethyl acrylate,2-(N,N-diethylamino)-ethyl acrylate and oleic or ricinoleic acidacrylate. U.S. Pat. No. 4,145,319 describes a water-reducible alkydresin derived in part from an ester of an alpha, beta-ethylenicallyunsaturated carboxylic acid of a polyesterified polyol containing atleast two hydroxy groups, e.g., an acrylic or methacrylic acid ester ofpentaerythritol, dipentaerythritol or tripentaerythritol.

Since the acrylic and methacrylic acid esters of multifunctional polyolsheretofore known are obtained from the direct esterification of the acidand polyol reactants, the resulting esters inevitably are mixtures ofmono- and polyacrylic and methacrylic acid esters, up to the entirenumber of hydroxyl groups originally present in the starting polyol.

SUMMARY OF THE INVENTION

In accordance with the present invention, an alpha, beta-ethylenicallyunsaturated monoester is provided which can be represented by thegeneral formula: ##STR1## in which group R₁ is hydrogen or a methylgroup and R₂ is either the group ##STR2## wherein R₃ is hydrogen or anon-functional organic group, preferably a lower alkyl group such asmethyl or ethyl, or R₂ is the group ##STR3##

Monoesters of a pentaerythritol orthoester can be prepared by theesterification of acrylic acid, methacrylic acid or corresponding acylhalide thereof with a pentaerythritol orthoester as in the equation:##STR4##

In the above, R₁ and R₃ have the same meanings given above and X ishydroxyl or halogen. When the acid halide is employed, it is generallypreferred to include an acid receptor in the reaction medium to take upthe coproduced haloacid.

Alternatively, the monoesters of pentaerythritol orthoester can beprepared by transesterifying the orthoester with an acrylic ormethacrylic acid ester accompanied by the distillation of theco-produced hydroxyl compound as in the equation: ##STR5##

As a third alternative, the monoesters of pentaerythritol orthoester canbe prepared by reacting a monobromo pentaerythritol orthoester withcuprous acrylate or cuprous methacrylate as in the equation: ##STR6##

In the above, R₁ and R₃ have the same meanings given above and R₄ is ahydrocarbyl group, preferably a lower alkyl group such as methyl orethyl.

Monoesters of pentaerythritol can be readily prepared by hydrolysis ofthe monoesters of pentaerythritol orthoester as in the equation:##STR7##

Unlike the multifunctional polyol derivatives known in the art anddescribed above, the monoesters herein are capable of providing highmolecular weight polymers due to their lack, or minimization, of chaintransfer hydrogens. Accordingly, further in accordance with the presentinvention, the acrylate and methacrylate monoesters of pentaerythritoland pentaerythritol orthoesters can be homopolymerized or copolymerizedwith other ethylenically unsaturated monomers to provide relatively highmolecular weight water soluble resins which are useful as thickeners,suspension agents, flocculants, and the like. The relatively lowmolecular weight resins impart advantageous wetting and adhesionproperties to coating compositions formulated therewith and can becrosslinked, for example, with isocyanates and polyisocyanates, toprovide industrially useful thermosetting coatings.

Another important use of the orthoesters herein is as latentcrosslinkers for emulsion polymers and latices.

The conditions under which the various esterification,transesterification, hydrolysis and polymerization reactions referred toabove are carried out are themselves well known and do not constitute apart of the invention herein per se.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The orthoester of pentaerythritol or monobromo pentaerythritol can bereadily and conveniently obtained by reacting pentaerythritol ormonobromo pentaerythritol with an orthoester of the formula R₃ C(OR₅)₃in which R₃ has the same meaning given above and R₅ is a lower alkylgroup, preferably a methyl or ethyl group, in the presence of a protondonor such as a strong mineral or organic acid accompanied bydistillation of the co-produced lower alkanol as in the equation:##STR8##

In the above equation, X represents a hydroxyl group or a halogen atom.

The pentaerythritol orthoester is esterified or interesterified as shownin the equations above to provide the acrylate and/or methacrylatemonoester which can thereafter be hydrolyzed, if desired, to thecorresponding pentaerythritol monoester.

The monoester can be polymerized alone or together with one or moreethylenically unsaturated monomers polymerizable therewith. The relativeproportions of acrylic/methacrylic monoester to such other monomers withwhich the former can be copolymerized can vary widely. For someapplications, the amount of interpolymerized comonomer should not be sohigh as to significantly reduce the water soluble properties of theresulting resins. Among the ethylenically unsaturated monomers which canbe copolymerized with the monoesters of this invention are those of thegeneral formula: ##STR9## wherein R₆ and R₇ each are representative ofsuch groups as hydrogen, lower acyclic, especially methyl, ethyl, propyland vinyl, lower cycloaliphatic, especially cyclohexyl and cyclohexenyl,aryl, especially phenyl, carboxyl, lower alkyl carboxyl, acetoxy, loweralkanoyloxy amido, acetamido and the like. Ethylenically unsaturatedmonomers conforming to such formula are ethylene, propylene, butene-1,vinyl cyclohexane, vinyl cyclohexene, styrene, vinyl styrene, vinyltoluene, acrylic acid, methacrylic acid, vinyl formate, vinyl acetate,vinyl propionate, vinyl butyrate, crotonic acid, itaconic acid, vinylfluoride, vinyl chloride, vinylidene fluoride, vinylidene chloride,tetrafluoroethylene, acrylamide, methacrylamide, methacrylonitrile,acrolein, methyl vinyl ether, ethyl vinyl ether, vinyl ketone, ethylvinyl ketone, allyl acetate, allyl propionate, diethyl maleate, etc.

The monoesters herein, and if present, other monomers copolymerizabletherewith, can be readily polymerized in a known manner employing any ofthe free radical polymerization catalysts heretofore used in thepolymerization of ethylenic monomers, e.g., inorganic peroxides such ashydrogen peroxide, sodium perchlorate and sodium perborate, inorganicpersulfates such as sodium persulfate, potassium persulfate and ammoniumpersulfate and reducing agents such as sodium bisulfite.

The homopolymers and copolymers of the present invention can berepresented by the general formula: ##STR10## wherein R₁, R₂, R₆ and R₇each have the same meanings given above and the sum of theinterpolymerized units m is at least about 10, the sum of theinterpolymerized units n is equal to zero or greater than 1, the sum ofm+n is from about 10 to about 10,000 and preferably from about 100 toabout 500 and the ratio of m to n is from about 100:1 to about 1:100 andpreferably, from about 10 to 1 to about 1 to 10.

The following examples are further illustrative of the invention.

EXAMPLE 1

This example illustrates the preparation of the starting hydroxymethylpentaerythritol orthoester.

In a large sublimation apparatus equipped with a side arm are mixed: 6.8g (0.05 mole) pentaerythritol, 7.4 g (0.05 mole) triethyl orthoformate,150 ml dioctyl phthalate (DOP) and a trace of anhydrousp-toluenesulfonic acid. Magnetic stirring is begun vigorously. Thesublimator is immersed in an oilbath at 140° C. After 2.5 molequivalentsof ethanol have been collected, the bath temperature is raised to 195°C., vacuum is applied to the apparatus (0.05 mm Hg) and the cold fingeris cooled with a methanol-Dry Ice mixture to about -50° C. After about15 minutes, crystals have collected on the cold finger, the DOP solutionhas cleared and some DOP has distilled. At this point, the reaction isstopped. The crystals are washed with hexane to remove DOP, anddissolved in chloroform leaving behind any polymer formed. An additionalcrop of crystals can be recovered from the distilled DOP in a similarmanner. The alcohol is recrystallized from benzene, avoiding prolongedheating.

The resulting product can be represented by the structural formula:##STR11##

4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane

Yield: 3.6 g (50%)

EXAMPLE 2

This example illustrates the preparation of acryloxy methyl orthoesterof pentaerythritol by reaction of the hydroxy-methyl pentaerythritolorthoester prepared as in Example 1 with acryloyl chloride.

4-Hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane (4.2 g, 30 mmole) isdissolved in 30 ml dry tetrahydrofuran in the presence of a trace of3,5-di-t-butylcatechol and 30 ml (0.3 mmole) of dry triethyl amine at 0°C. Acryloyl chloride (2.7 g, 30 mmole) dissolved in 10 mltetrahydrofuran is added slowly. The mixture is stirred for anadditional hour. The precipitate is filtered off and the solvent isevaporated. The residue is dissolved in chloroform and the solution isrun through a silicagel column to remove any possible residual quantityof triethylamine hydrochloride which causes polymerizations in attemptsto recrystallize the acrylate. The obtained product (m.p. 86°-87° C.) isrecrystallized from hexane and can be represented by the structuralformula: ##STR12##

4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane

Yield: 3.0 g (53%)

EXAMPLE 3

This example illustrates another procedure for preparing acryloxy methylorthoester of pentaerythritol, i.e., the reaction of4-bromomethyl-2,6,7-trioxabicyclo[2.2.2]octane with cuprous acrylate.

A. Preparation of Monobromopentaerythritol

The synthesis of monobromopentaerythritol is described by S. Wawzonek,et al., Org. Synth. Vol. IV, 681 (1963) which is incorporated bereference herein. The synthesis described herein is improved over theprocedure described by Wawzonek, et al. in adding acetic anhydride tothe reaction mixture which increases the hydrobromic acid concentrationfrom 48% to 66%. The product can then be purified by taking advantage ofthe difference in solubility of the starting material and the productsformed.

In a 2 liter, three-necked flask equipped with a reflux condenser and anaddition funnel are placed 200 g pentaerythritol (1.47 mole) and 16 ml48% hydrobromic acid in about 500 ml glacial acetic acid. The mixture isrefluxed for about one-half hour until all pentaerythritol is dissolved.Then, 170 ml 48% hydrobromic acid are added, followed by 310 ml aceticanhydride and the mixture is refluxed for 3 hours. Then, 94 ml 48%hydrobromic acid followed by 150 ml acetic anhydride are added and themixture is refluxed for an additional 3 hours. The acetic acid is thenremoved as completely as possible on a rotary evaporator. Ethanol (95%,750 ml) and 17 ml 48% hydrobromic acid are then added to the residue.The flask is equipped with 1 m Vigreux column and the azeotrope ethylacetate/ethanol is slowly distilled off. When 500 ml distillate has beencollected, an additional 750 ml 95% ethanol is added and thedistillation is continued until about 400 ml is left over. Aftercooling, the precipitated pentaerythritol is filtered off. The solventis evaporated and the residue is dissolved in water. The aqueous phaseis extracted twice with carbon tetrachloride and twice with ether. Thewater is evaporated on the rotary evaporator and the last traces ofwater are removed by azeotropic distillation with toluene using aDean-Stark trap. The solid is recrystallized from chloroform containing10% acetonitrile. The first crop yielded 190 g monobromopentaerythritol.The total yield is 70%.

Monobromopentaerythritol (m.p. 72° C./lit. 76° C.) is very slightlysoluble in chloroform, very soluble in ethanol, sec. butanol andacetonitrile, and insoluble in ether.

B. Preparation of 4-Bromomethyl-2,6,7-Trioxabicyclo[2.2.2]Octane

Monobromopentaerythritol from A (10 g, 0.05 mole) and 9 mltriethylorthoformate (0.05 mole) are mixed in a sublimation apparatusequipped with a side arm. The mixture is heated to about 100° C. withmagnetic stirring, and 1,5 equivalents of ethanol are allowed to distillout. Then about 100 ml dioctyl phthalate and a trace of anhydrousp-toluenesulfonic acid are added. Under vacuum the mixture is heated toabout 140°-150° C. Periodically the collected crystals are removed fromthe cold finger. After about 3 hours no more compound sublimes. Theyield of 4-bromoethyl-2,6,7-trioxabicyclo[2.2.2]octane is 6.5 g (60%).

C. Preparation of Cuprous Acrylate

Cupric acrylate (12 g, 0.058 mole) is mixed with about 250 ml dryacetonitrile, 30 g (0.5 mole) copper foil, 5 ml of acrylic acid, a fewmolecular sieves and a trace of radical inhibitor. The reaction mixtureis stirred for 24 hours under nitrogen atmosphere until all the bluecolor disappears. Some white precipitate is formed. This precipitate andthe solution are decanted from the remaining copper in a glovebag undernitrogen atmosphere and added to approximately 600 ml dry ether. Theformed white precipitate is filtered off and dried, still undernitrogen. The yield of cuprous acrylate is 12.6 g (81%).

D. Preparation of 4-Acryloxymethyl-2,6,7-Trioxabicyclo[2.2.2]Octane

Cuprous acrylate from C. (0.017 g, 0.08 mole) and4-bromomethyl-2,6,7-trioxabicyclo[2.2.2]octane from B. (12.5 g, 0.06mole) are dissolved in 100 ml dry pyridine under nitrogen atmosphere.Some triethylamine radical inhibitor is added. The mixture is refluxedfor 3 hours. The pyridine is completely evaporated. The green solids areground up and placed in a soxhlet for extraction with hexane for 24hours. The hexane is evaporated and the solids are dissolved inchloroform. The solution is passed through a short silicagel column toremove any remaining copper salts. The acrylate is recrystallized fromhexane. Long white needles of4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane are recovered.

Yield: 6 g (60%)

EXAMPLE 4

This example illustrates the process of hydrolyzing4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and the productsresulting therefrom.

4-Acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane (3 g) is mixed with 30ml distilled water at room temperature. The mixture becomes homogeneousafter 1/2 hour. The NMR spectrum indicates only partial hydrolysis hastaken place, the partial hydrolyzate having the structure: ##STR13## Thereaction mixture is then heated to 70° C. The NMR spectrum of thereaction mixture is checked periodically to follow the reaction. After4.5 hours the reaction is complete. The water and formed formic acid areevaporated and the reaction product is dried under vacuum. A glue-likematerial is obtained which does not crystallize after 3 days at -10° C.The material can be pulled into fibers several feet long. The productpentaerythritol monoacrylate which can be represented by the structure##STR14## is insoluble in all common organic solvents includingchloroform and acetonitrile.

EXAMPLE 5

The procedure of Example 2 is substantially repeated except that4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane is reacted withmethacroyl chloride to provide the orthoester (m.p. 89°-91° C.):##STR15##

4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane

Yield: 45%

EXAMPLE 6

This example illustrates the partial and complete hydrolysis of theorthoester product of Example 5.

4-Methyacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane (30 mg) is mixedwith 1 ml of water. After 2 hours at 60° C. dissolution occurs and theNMR spectrum indicates partial hydrolysis to: ##STR16## After 20 hoursat 60° C., complete hydrolysis occurs to pentaerythritolmonomethacrylate which can be represented by the structural formula##STR17##

EXAMPLE 7

This example illustrates the preparation of1-methyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane.

Pentaerythritol (13.6 g, 0.1 mole), triethyl orthoformate (16 g, 0.1mole), a trace of p-toluenesulfonic acid and 100 ml dioctyl phthalateare mixed in a flask at 140° C. After the theoretical amount of ethanolhas distilled out, the temperature is raised to 180°-190° C. and thepressure is reduced to <0.5 mm Hg. A white product crystallized in thecondensor and is recrystallized from benzene. The product orthoester(m.p. 112° C.) can be represented by the structural formula ##STR18##

1-methyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane

Yield: 8.0 g (50%)

EXAMPLE 8

This example illustrates the conversion of the product orthoester ofExample 7 to the corresponding methacryloxymethyl orthoester derivative.

Methacryloyl chloride (6.0 g, 0.06 mole) in 200 ml tetrahydrofuran isslowly added to a flask containing 9.0 g (0.06 mole), 60 mltriethylamine (0.6 mole) and a trace of radical inhibitor in 50 mltetrahydrofuran at 0° C. The mixture is stirred for 1 hour, theprecipitate is filtered off and the solvent is evaporated. The residuedissolved in chloroform is passed through a silicagel column andrecrystallized from hexane. The product orthoester (m.p. 86° C.) can berepresented by the structural formula ##STR19##

1-methyl-4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane

Yield: 5.4 g (40%)

EXAMPLE 9

This example illustrates the hydrolysis of the orthoester product ofExample 8.

1-Methyl-4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane (50 mg)is mixed with 1 ml water. After 2 hours dissolution occurs and theresulting solution contains the partially hydrolyzed product of thestructure ##STR20##

The foregoing product does not hydrolyze further to pentaerythritolmonomethacrylate even at higher temperature. Addition of acid results indecomposition of the material.

EXAMPLE 10

This example illustrates the polymerization of4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane.

To a 1 g benzene solution of4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane is added 20 mgazobisisobutyronitrile (AIBN) initiator. The solution is purged withargon and heated at 80° C. for 6 hours. At this time, the solution isextremely viscous and cools to a brittle clear glass. The resultingpolymer, poly(4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane) whichis represented by the structure ##STR21## has an inherent viscosity(0.1%, chloroform) of 0.53 dl.g.⁻¹

EXAMPLE 11

This example illustrates the hydrolysis ofpoly(4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane) topoly(pentaerythritol monoacrylate).

Poly(4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]-octane) (50 mg) ismixed with 1 ml deuterated water in an NMR tube with 4 mole % formicacid. The heterogeneous mixture is heated to 70° C. for 3 hours untilhomogeneous. The NMR spectrum indicates only partial hydrolysis, to apolymer of the structure ##STR22##

After 2 weeks at room temperature the following NMR spectrum indicatedthat complete hydrolysis had taken place to poly(pentaerythritolmonoacrylate) ##STR23##

EXAMPLE 12

This example illustrates the polymerization of4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane.

The polymerization is carried out substantially in accordance with theprocedure described in Example 10. The resulting polymer,poly(4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane), which canbe represented by the formula ##STR24## is soluble in dimethylsulfoxide.

EXAMPLE 13

The orthoester product of Example 8 is polymerized in much the samemanner as described in Example 10. The resulting polymer,poly(1-methyl-4-methacryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane),which can be represented by the formula ##STR25## is soluble inchloroform and acetone.

EXAMPLE 14

This example illustrates the polymerization of pentaerythritolmonoacrylate (Example 4).

4-Acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane, 1 g, is mixed with 10ml redistilled water. The bicyclic orthoester is hydrolyzed topentaerythritol monoacrylate at 60° C. for 4 hours. The only by-productformed is formic acid which does not interfere with the radicalpolymerization. The water solution is divided in several vials andinitiator is added. When potassium persulfate and sodium thiosulfate arechosen as initiating system, a Y-tube is used. The mixture is degassedtwice and then the vials are sealed. The pentaerythritol monoacrylate ispolymerized under the conditions described in Table I below. For themeasurement of the inherent viscosity, the solutions are diluted to 10ml. The polymers, which have a structure as shown in Example 11, areisolated by freeze-drying.

                                      TABLE I                                     __________________________________________________________________________    POLYMERIZATION OF PENTAERYTHRITOL MONOACRYLATE                                Amount of                                                                     Pentaerythritol                                                                       Initiator    Total     t.sup.b                                        Monoacrylate                                                                          K.sub.2 S.sub.2 O.sub.8                                                              Na.sub.2 S.sub.2 O.sub.3                                                            Volume                                                                             Method.sup.a                                                                       (sec)                                                                            n.sub.inh.sup.b                                                                  Remarks                                  __________________________________________________________________________    250 mg  5 mg = --    4 ml UV/45°                                                                      -- -- contains gel                                     1,5 mole %                                                            250 mg  5 mg = --    4 ml 80°                                                                         -- -- contains gel                                     1,5 mole %                                                            190 mg  5 mg = --    10 ml                                                                              UV/45°                                                                      -- .sup.c                                                                           viscous                                          2 mole %                                                              380 mg  5 mg = --    10 ml                                                                              UV/45°                                                                      140.8                                                                            0.25                                                1 mole %                                                              190 mg  0.25 mg =                                                                            --    2 ml UV/45°                                                                      241.9                                                                            0.79                                                0.1 mole %                                                            190 mg  0.12 mg =                                                                            --    2 ml UV/45°                                                                      157.8                                                                            0.57                                                0.025 mole %                                                          190 mg  5 mg = 5 mg =                                                                              2 ml 25°                                                                         118.9                                                                            0.45                                                1 mole %                                                                             2 mole %                                                       190 mg  0.5 mg =                                                                             0.5 mg =                                                                            2 ml 25°                                                                         134.7                                                                            0.49                                                0.1 mole %                                                                           0.2 mole %                                                     190 mg  0.25 mg =                                                                            0.25 mg =                                                                           2 ml 25°                                                                         333.2                                                                            0.96                                                0.05 mole %                                                                          0.1 mole %                                                     __________________________________________________________________________     .sup.a All runs for 16 hours and with stirring except for first two, all      runs went to 100%.                                                            .sup.b t = flow time in an Ostwald viscosimeter, solvent is water, t.sub.     = 53.6 sec., 30° C., solutions diluted to 10 ml.                       .sup.c Polymers were isolated and impossible to redissolve.              

EXAMPLE 15

This example illustrates the polymerization of the partially hydrolyzedmonomer produced substantially in accordance with the hydrolysis processdescribed in Example 9.

Polymerization of this compound follows generally the same proceduredescribed in Example 14. The resulting polymer, which conforms to thepolymeric structure given in Example 11, precipitates out of the wateras it is formed. After drying, the polymer is dissolved inhexafluoroisopropanol and precipitated in ether. A white powder isobtained.

EXAMPLES 16-30

The following examples, the conditions and results of which are setforth in Table II below, are further illustrative of homopolymerizationsof the orthoester monomers of the present invention.

                                      TABLE II                                    __________________________________________________________________________    HOMOPOLYMERIZATION OF VARIOUS ORTHOESTER MONOMERS                               Orthoester                                                                          Amount of              Initiator      Yield                           e Monomer                                                                             Monomer                                                                              Conditions                                                                          Time                                                                              Initiator                                                                           Amount Solvent %   n.sub.inh                                                                         Remarks                 __________________________________________________________________________    a       200 mg 5                                                                             UV/40°                                                                       20 hrs                                                                            benzoyl                                                                             1 mole %                                                                             benzene 90  --  not soluble                                      peroxide                     (gel)                   a       200 mg 5                                                                             UV/40°                                                                       20 hrs                                                                            AIBN  1 mole %                                                                             acetone ?   --  not soluble                                                                   (solid)                 a       200 mg 5                                                                             UV/40°                                                                        3 hrs                                                                            AIBN  1 mole %                                                                             benzene  0  --                          a       200 mg 5                                                                             UV/40°                                                                        8 hrs                                                                            AIBN  1 mole %                                                                             benzene 10  --  not soluble             a       250 mg 5                                                                             UV/40°                                                                       20 hrs                                                                            AIBN  1 mole %                                                                             benzene 90  --  not soluble                                                                   (gel)                   a       200 mg 5                                                                             80°                                                                          20 hrs                                                                            AIBN  1 mole %                                                                             benzene 85  --  not soluble             a       202 mg 5                                                                             UV/40°                                                                       16 hrs                                                                            AIBN  1 mole %                                                                             (CF.sub.3).sub.2 CHOH                                                                 100                             a       200 mg 5                                                                             UV/40°                                                                       16 hrs                                                                            AIBN  0.25 mole %                                                                          Sulfolane                                                                             100     polymer does                                                                  not completely                                                                redissolve                                                                    after precipi-                                                                tation                  a       200 mg 5                                                                             UV/40°                                                                       16 hrs                                                                            AIBN  1 mole %                                                                             Sulfolane                                                                             98  0.2.sup.d                   a       200 mg 5                                                                             UV/40°                                                                       16 hrs                                                                            AIBN  0.5 mole %                                                                           Sulfolane                                                                             100 0.2.sup.d                   b        50 mg 11                                                                            UV/40°                                                                       20 hrs                                                                            AIBN  5 mole %                                                                             benzene 30      not soluble             b       200 mg 11                                                                            UV/40°                                                                       20 hrs                                                                            AIBN  5 mole %                                                                             sulfolane                                                                             75  0.92.sup.e                                                                        soluble                 c       230 mg 13                                                                            UV/40°                                                                       20 hrs                                                                            AIBN  1 mole %                                                                             benzene 87  0.82.sup.e                                                                        not soluble             c       230 mg 13                                                                            UV/40°                                                                       20 hrs                                                                            AIBN  3 mole %                                                                             benzene 95  0.52.sup.e                                                                        not soluble             c       230 mg 13                                                                            UV/40°                                                                       20 hrs                                                                            AIGN  3 mole %                                                                             (CF.sub.3).sub.2 CHOH                                                                 68      soluble, part-                                                                ially                   __________________________________________________________________________                                                          decomposed               acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane                               methacryloxymethyl2,6,7-trioxabicyclo[2.2.2]octane                            methyl4-methacryloxymethyl-2,6,7-trioxiabicyclo[2.2.2]octane                  herent viscosity measured in Ostwald viscosimeter in sulfolane at             30° C.                                                                 herent viscosity measured in hexafluoroisopropanol at 30° C.      

EXAMPLES 31-36

These examples illustrate the copolymerization of4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane with a variety ofvinyl comonomers.

Benzene is dried over sodium and distilled just before use. Acetone wasrefluxed over potassium permanganate, distilled and redistilled overcalcium hydride. Hexafluoroisopropanol was distilled from calciumhydride. Monomer, eventual comonomer, initiator and solvent are mixed inan ampoule, cooled to -78°, degassed, thawed, cooled and degassed again.Then the ampoule is sealed. At the end of the polymerization, attemptsare made to dissolve the polymer and the whole is precipitated inhexane. The polymer is filtered off, dried and weighed.

Additional conditions, and the results, of each copolymerization are setforth in Table III as follows:

                                      TABLE III                                   __________________________________________________________________________    POLYMERIZATION OF 4-ACRYLOXYMETHYL-2,6,7-                                     TRIOXABICYCLO[2.2.2]OCTANE                                                    Amount              Mole ratio    Mole                                        Orthoester                                                                          Vinyl  Amount Monomer       Ratio in                                    Monomer                                                                             Comonomer                                                                            Comonomer                                                                            Comonomer                                                                            Yield  Polymer                                     __________________________________________________________________________    200 mg                                                                              methyl 43 mg  66/33  120 mg/49%                                                                           45/55                                             acrylate                                                                200 mg                                                                              methyl 86 mg  50/50  275 mg/96%                                                                           40/60                                             acrylate                                                                200 mg                                                                              methyl 50 mg  66/33  221 mg/88%                                                                           56/44                                             methacrylate                                                            200 mg                                                                              methyl 100 mg 50/50  252 mg/84%                                                                           41/59                                             methacrylate                                                            200 mg                                                                              p-methoxy-                                                                           67 mg  66/33  113 mg/45%                                                                           50/50                                             styrene                                                                 200 mg                                                                              p-methoxy-                                                                           135 mg 50/50  149 mg/49%                                                                           40/60                                             styrene                                                                 __________________________________________________________________________     Polymerization catalyst: 1 mole % azobisisobutyronitrile                      Polymerization conditions: Ultraviolet (UV) light at 40° for 16        hours                                                                    

EXAMPLE 37

This example illustrates the use of an ester herein, namely,4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane, in the preparation ofa vinyl-acrylic copolymer textile crosslinking latex.

The following formulation was prepared:

    ______________________________________                                        Component                 Quantity                                            ______________________________________                                        Vinyl Acetate             360    g                                            Butyl Acrylate            6.4    g                                            Acrylic Acid              0.5    g                                            Acrylamide                0.3    g                                            Duponol (Du Pont lauryl sulfate surfactant)                                                             3.0    g                                            Sodium Persulfate         100    mg                                           Sodium Thiosulfate        100    mg                                           Ferrous Sulfate           0.5    mg                                           Water                     52     ml                                           4-Acryloxymethyl-2,6,7-Trioxabicyclo[2.2.2]                                                             400    mg                                           Octane                                                                        ______________________________________                                    

Into a flask under nitrogen atmosphere are mixed half the amounts ofindicated vinyl acetate, butyl acrylate, acrylic acid acrylamide and4-acryloxymethyl-2,6,7-trioxabicyclo[2.2.2]octane, and the water andlauryl sulfate surfactant. The mixture is heated to 30° C. Half theindicated amount of sodium persulfate and sodium thiosulfate are addedtogether with the ferrous sulfate. The temperature rises to 39° C. Aftercooling to 30° C., the remainder of all the reagents are added. Thetemperature rises to 37° C. Under continuous stirring, the reactionmixture, a polymer emulsion, is heated to 65° C. for 1 additional hourand thereafter the emulsion is brought to a pH of about 6 with ammoniumhydroxide.

By way of evaluating the emulsion, two films were cast therefrom. Thefilms (2 mil) on glass were hazy and when dry could not be lifted intactfrom the plate. The first film dried 48 hours at room temperature wasattacked by acetone and while not completely dissolved, was softened andcould easily be rubbed from the plate. Baking of the second film (airdried 24 hours) in an oven at 80° C. for 24 hours resulted in a visuallyunchanged sample which was observed to be resistant to acetone. Whilethe film obviously absorbed acetone (blushed) it was not softened orweakened and was resistant to abrasion, even while soaking in thesolvent. This evaluation demonstrates the utility of the foregoingemulsion as a latent cross-linking site for latex films.

What is claimed is:
 1. A polymer comprising an alpha, beta-ethylenicallyunsaturated monoester of the general formula ##STR26## in which R₁ ishydrogen or a methyl group and R₂ is the group ##STR27## wherein R₃ ishydrogen or a lower alkyl group.
 2. A polymer comprising the alpha,beta-ethylenically unsaturated monoester of claim 1 wherein R₁ ishydrogen and R₂ is the group ##STR28##
 3. A polymer comprising thealpha, beta-ethylenically unsaturated monoester of claim 1 wherein R₁ isa methyl group and R₂ is the group ##STR29##
 4. A polymer of claim 1 ofthe formula ##STR30## wherein n is from about 100 to about
 500. 5. Apolymer of claim 1 of the formula ##STR31## wherein n is from about 100to about
 500. 6. A polymer of claim 1 of the general formula ##STR32##in which R₁ is hydrogen or a methyl group, R₂ is the group ##STR33##wherein R₃ is hydrogen or lower alkyl group, R₆ and R₇ are eachhydrogen, lower acyclic, lower cycloaliphatic, aryl, carboxyl, loweralkyl carboxyl, acetoxy, lower alkanoyloxy, amido or acetamido, the sumof the interpolymerized units m is at least about 10, the sum of theinterpolymerized units n is equal to zero or greater than 1, the sum ofm+n is from 10 to about 10,000 and the ratio of m to n is from about100:1 to about 1:100.
 7. A polymer of claim 1 of the general formula##STR34## in which group R₁ is hydrogen or a methyl group, R₂ is thegroup ##STR35## wherein R₃ is hydrogen or a lower alkyl group, the sumof the interpolymerized units m is at least about 10, the sum of theinterpolymerized units n is equal to zero or greater than 1, the sum ofm+n is from about 10 to about 10,000 and the ratio of m to n is fromabout 100:1 to about 1:100 and in which the unit ##STR36## is derivedfrom ethylene, propylene, butene-1, vinyl cyclohexane vinyl cyclohexene,styrene, vinyl styrene, vinyl toluene, acrylic acid, methacrylic acid,vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, crotonicacid, itaconic acid, vinyl fluoride, vinyl chloride, vinylidenefluoride, vinylidene chloride, tetrafluoroethylene, acrylamide,methacrylamide, methacrylonitrile, acrolein, methyl vinyl ether, ethylvinyl ether, vinyl ketone, ethyl vinyl ketone, allyl acetate, allylpropionate or diethyl maleate.
 8. The polymer of claim 6 in which thesum of m+n is from about 100 to about
 500. 9. The polymer of claim 6 inwhich the ratio of m to n is from about 10 to 1 to about 1 to 10.